Preparation of polyarylate polymers of hydroxyaryl-substituted 1,6-diaza [4.] spirodilactams

Abstract

High molecular weight polyarylate polymers comprise alternating moieties derived from an aromatic dicarboxylic acid halide, with moieties derived from a hydroxyaryl-substituted 1,6-diaza [4.4] spirodilactam compound and, optionally, with moieties derived from a di(hydroxyphenyl) compound are prepared by interfacial polymerization in an aqueous-organic medium containing an alcohol.

What is claimed is: 
     
       1. An interfacial polymerization process for preparing high molecular weight polyarylates which comprises reacting under interfacial polyarylate-forming conditions, (a) a hydroxyaryl-substituted [4.4] spirodilactam having the spiro ring nitrogen atoms at the 1l- and 6-positions of the spirodilactam ring having a hydroxyaryl substituent on each of said spiro ring nitrogen atoms with (b) an aromatic diacid halide with or without, (c) a di(hydroxyphenyl) compound, in the presence of an aqueous caustic solution containing an alkali or alkaline earth metal hydroxide, an inert water immisible organic solvent, which substantially dissolves the organic reactants and the polyarylate, and deemulsifying agent which does not substantially dissolve the polyarylate. 
     
     
       2. The process according to claim 1 wherein the organic solvent is a chlorinated aliphatic hydrocarbon. 
     
     
       3. the process according to claim 1 or 2 wherein the chlorinated aliphatic hydrocarbon is chloroform. 
     
     
       4. The process according to claim 1 or 2 wherein a catalyst is also present. 
     
     
       5. The process according to claim 4 wherein the catalyst is a tertiary amine or quaternary ammonium salt. 
     
     
       6. The process according to claim 5 wherein the catalyst is triethylbenzylammonium chloride. 
     
     
       7. The process according to claim 1 or 2 wherein the deemulsifying agent is a lower alkanol. 
     
     
       8. The process according to claim 7 wherein the alcohol is isopropanol. 
     
     
       9. The process according to claim 1 or 2 wherein the reaction is conducted at temperature in the range of from about 0° C. to about 100° C. 
     
     
       10. The process according to claim 9 wherein the temperature is from about 0° C. to about 35° C. 
     
     
       11. The process according to claim 1 or 2 wherein (a) and (c), when present, each is used in the form of a di(alkali metal) salt. 
     
     
       12. The process according to claim 1 wherein the deemulsifying agent is a lower alkanol and the organic solvent is a chlorinated aliphatic hydrocarbon. 
     
     
       13. The method according to claim 1 wherein the polymer comprises a first repeating segment of the formula ##STR10## with or without up to nine times the molar quantity of the first segment of a second repeating segment of the formula ##STR11## wherein R is aromatic of up to 15 carbon atoms and up to two aromatic rings, inclusive, R' is R or aliphatic of up to 10 carbon atoms, r is 0or 1, X is a direct valence bond or X is alkylene of up to 15 carbon atoms inclusive, oxy, thio, sulfonyl, carbonyl, dioxyphenylene, 2,2-di(oxyphenyl)propane, di(oxyphenyl) sulfone or dioxydiphenylene, R" is divalent arylene of up to 28 carbon atoms and from 1 to 2 aromatic rings, inclusive, Z independently is >C(X') 2  in which Z' independently is hydrogen, lower alkyl, lower halo or phenyl, or Z is such that two adjacent Z groups taken together form a ring system Z" of from 5 to 7 ring atoms, up to two of which are heteroatoms selected from nitrogen, oxygen or sulfur with the remainder of the ring atoms being carbon atoms, there being up to 15 carbon atoms in each Z", two of which form a bridge between the carbon atoms connected by the adjacent Z groups, X' is a direct valence bond or X' is alkylene of up to 8 carbon atoms inclusive, oxy, thio, sulfonly or carbonyl and G independently is hydrogen, lower alkylene or middle halo. 
     
     
       14. The process according to claim 13 wherein in the polymer is a polymer of the first repeating segment. 
     
     
       15. The process according to claim 14 wherein in the polymer each r is 0. 
     
     
       16. The process of claim 15 wherein in the polymer R" has a single aromatic ring. 
     
     
       17. The process according to any one of claims 13, 14, 15 or 16 wherein in the polymer Z is >C(Z') 2 . 
     
     
       18. The process of claim 17 wherein in the polymer R is phenylene. 
     
     
       19. The process of claim 18 wherein in the polymer Z is hydrogen. 
     
     
       20. The process of any one of claims 13, 14, 15 or 16 wherein in the polymer the carbon atoms through which R- is connected to the remainder of the polymer chain are meta or para to each other. 
     
     
       21. The process of claim 20 wherein in the polymer R is p-phenylene. 
     
     
       22. The process of any one of claims 13, 14, 15 or 16 wherein in the polymer adjacent Z groups are Z". 
     
     
       23. The process of claim 22 wherein in the polymer R is phenylene. 
     
     
       24. The process of claim 23 wherein in the polymer Z- is benzo. 
     
     
       25. The process of claim 22 wherein in the polymer R is p-phenylene. 
     
     
       26. The process of claim 13 wherein in the polymer is a polymer of said first and second repeating segments. 
     
     
       27. The process of claim 26 wherein in the polymer G is halo. 
     
     
       28. The process of claim 27 wherein in the polymer G is bromo. 
     
     
       29. The process of claim 28 wherein in the polymer each r is 0. 
     
     
       30. The process of claim 29 wherein in the polymer R- has a single aromatic ring. 
     
     
       31. The process of claim 30 wherein in the polymer X- is 2,2-propylene. 
     
     
       32. The process of claim 31 wherein in the polymer Z is >C(Z-) 2 . 
     
     
       33. The process of claim 32 wherein in the polymer R is phenylene. 
     
     
       34. The process of claim 33 wherein the polymer Z- is hydrogen. 
     
     
       35. The process of any one of claims 26, 27, 28, 29, 30, 31, 32, 33 or 34 wherein in the polymer the carbon atoms through which R- is connected to the remainder of the polymer chain are meta or para to each other. 
     
     
       36. The process of claim 35 wherein in the polymer R is p-phenylene. 
     
     
       37. The process of any one of claims 26, 27, 28, 29, 30 or 31 wherein in the polymer adjacent Z groups are Z-. 
     
     
       38. The process of claim 37 wherein in the polymer Z- is benzo. 
     
     
       39. The process of claim 38 wherein in the polymer R is p-phenylene. 
     
     
       40. The process of claim 13 or 26 wherein in the polymer the second segment is present at up to twice the molar quantity of the first segment.